CN114276642B - Silicon core tube resistant to environmental stress cracking and preparation method thereof - Google Patents
Silicon core tube resistant to environmental stress cracking and preparation method thereof Download PDFInfo
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- CN114276642B CN114276642B CN202111503608.2A CN202111503608A CN114276642B CN 114276642 B CN114276642 B CN 114276642B CN 202111503608 A CN202111503608 A CN 202111503608A CN 114276642 B CN114276642 B CN 114276642B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000005336 cracking Methods 0.000 title claims abstract description 23
- 230000006353 environmental stress Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 49
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 49
- 239000012767 functional filler Substances 0.000 claims abstract description 32
- 239000011241 protective layer Substances 0.000 claims abstract description 30
- 239000012792 core layer Substances 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- -1 allyl diethyl malonate Chemical compound 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 239000004595 color masterbatch Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000006229 carbon black Substances 0.000 claims description 17
- 239000002121 nanofiber Substances 0.000 claims description 17
- 239000010410 layer Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 239000011246 composite particle Substances 0.000 claims description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 9
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 9
- 229920002050 silicone resin Polymers 0.000 claims description 9
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- GDWAYKGILJJNBB-UHFFFAOYSA-N diethyl 2-prop-2-enylpropanedioate Chemical compound CCOC(=O)C(CC=C)C(=O)OCC GDWAYKGILJJNBB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 6
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical group C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 5
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- IRCSIGNHSFZBRR-UHFFFAOYSA-N dioctyltin 6-methylheptyl 2,2-bis(sulfanyl)acetate Chemical group C(CCCCCCC)[Sn]CCCCCCCC.SC(C(=O)OCCCCCC(C)C)S IRCSIGNHSFZBRR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 239000007983 Tris buffer Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 7
- 230000035882 stress Effects 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PIRIAZVDIOKRIR-UHFFFAOYSA-N dioctyltin;6-methylheptyl 2-hydroxyethanedithioate Chemical compound CC(C)CCCCCSC(=S)CO.CCCCCCCC[Sn]CCCCCCCC PIRIAZVDIOKRIR-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Abstract
The invention relates to the technical field of silicon core tubes, in particular to an environment stress cracking resistant silicon core tube and a preparation method thereof, and the environment stress cracking resistant silicon core tube comprises a synchronously extruded and compounded silicon core layer and an outer protective layer, wherein the outer protective layer comprises the following raw materials in parts by weight: 75-90 parts of modified high-density polyethylene, 2-5 parts of color master batch, 10-15 parts of functional filler, 1-3 parts of antioxidant, 1-3 parts of anti-aging agent and 1-2 parts of stabilizer, wherein the modified high-density polyethylene is allyl diethyl malonate melt grafting modified high-density polyethylene. The silicon core tube resistant to environmental stress cracking is prepared by modifying the matrix material high-density polyethylene and adding the functional filler, and has better environmental stress cracking resistance.
Description
Technical Field
The invention relates to the technical field of silicon core tubes, in particular to an environment stress cracking resistant silicon core tube and a preparation method thereof.
Background
The silicon core tube is an advanced optical cable protective sleeve for communication, and mainly comprises a color belt layer, a silicon core layer and an HDPE layer, and has the advantages of small friction factor, less pipe joint, rapid construction, no need of external large tube protection, permanent solid lubricant layer on the silicon core layer on the inner wall, unchanged friction performance and the like, so that the silicon core tube is widely applied to highways, city cables and the like as an optical cable threading tube.
With the rapid development of urban construction, the electric pole is not allowed to be erected through municipal construction, so that an underground laying mode is developed, and when the electric pole is laid underground, the silicon core tube protects the optical cable, so that the optical cable is free from external force, but the silicon core tube is extruded by external force such as an upper soil layer for a long time, slipping is easy to occur between wafers of high-density polyethylene of the silicon core tube, cracks are induced, and finally the silicon core tube is broken.
Disclosure of Invention
In view of the above, the invention aims to provide an environmental stress cracking resistant silicon core tube and a preparation method thereof, and the prepared silicon core tube has better environmental stress cracking resistance by modifying a matrix material high-density polyethylene and adding a functional filler.
The invention solves the technical problems by the following technical means:
the silicon core tube resistant to environmental stress cracking comprises a synchronously extruded composite silicon core layer and an outer protective layer, wherein the outer protective layer comprises the following raw materials in parts by weight: 75-90 parts of modified high-density polyethylene, 2-5 parts of color master batch, 10-15 parts of functional filler, 1-3 parts of antioxidant, 1-3 parts of anti-aging agent and 1-2 parts of stabilizer, wherein the modified high-density polyethylene is allyl diethyl malonate melt grafting modified high-density polyethylene.
Further, the functional filler takes white carbon black as a core, a polystyrene outer layer is wrapped outside the core, a fiber layer is further arranged between the polystyrene outer layer and the core, the fiber layer is formed by wrapping polyethylene nano fibers, and the thickness is 0.1-0.12mm.
According to the silicon core tube disclosed by the invention, the high-density polyethylene is grafted and modified by using the diethyl allylmalonate, the high-density polyethylene is converted into a branched structure from a linear structure, the introduced diethyl allylmalonate can increase entanglement of molecular chains among the high-density polyethylene, so that the movement among the molecular chains is increased, and the wafers are not easy to slip off, so that the defects in the prepared outer protection layer can be reduced to a certain extent, the prepared silicon core tube is more stable under the action of stress, and meanwhile, the added functional filler can firstly strengthen the mechanical property of a matrix material, and secondly, the fiber layer outside the core of the functional filler has a certain compressibility, so that the stress generated outside can be absorbed to a certain extent, meanwhile, the styrene outer layer of the functional filler is an elastic material, and the effect of buffering and absorbing the stress can be better realized by combining the fiber layer inside, so that the environment stress resistance of the prepared silicon core tube is improved.
In addition, the functional filler is added into the matrix material, when silver patterns are generated in the outer protective layer due to the stress effect, the silver patterns can be blocked after encountering the functional filler, so that the cracking probability is reduced to a certain extent.
Further, the outer protective layer comprises the following raw materials in parts by weight: 80 parts of modified high-density polyethylene, 2 parts of color master batch, 12 parts of functional filler, 2 parts of antioxidant, 2 parts of anti-aging agent and 1 part of stabilizer.
Further, the silicon core layer comprises the following raw materials in parts by weight: 20-30 parts of carrier resin, 45-55 parts of silicone resin, 5-10 parts of oleamide, 1-2 parts of lubricant, 2-5 parts of flame retardant FR-302C, 1-3 parts of compatilizer and 1-3 parts of antioxidant 1010.
Further, the silicon core layer comprises the following raw materials in parts by weight: 30 parts of carrier resin, 50 parts of silicone resin, 8 parts of oleamide, 2 parts of lubricant, 5 parts of flame retardant FR-302C, 3 parts of compatilizer and 10102 parts of antioxidant.
Further, the stabilizer is isooctyl dimercaptoacetate di-n-octyl tin, the lubricant is polyethylene wax, the antioxidant is phenyl tri (2, 4-di-tert-butyl) phosphite, and the antioxidant is 2, 4-trimethyl-1, 2-dihydroquinoline.
Further, the thickness of the silicon core layer is 0.2-0.3mm, and the thickness of the outer protective layer is 2-3mm.
In addition, the invention also discloses a preparation method of the silicon core tube resistant to environmental stress cracking, which comprises the following steps:
s1: according to the proportion, 1/2 mass of carrier resin is put into a high-speed stirrer, silicone resin and oleamide are added, the temperature is raised to 90-100 ℃ and stirred uniformly, then the temperature is raised to 115-120 ℃, compatilizer and lubricant are added, the high-speed stirring is carried out for 10-20min at a high temperature, flame retardant, antioxidant and the rest carrier resin are added, the stirring is continued for 20-30min, the heating is stopped, the stirring is continued until the mixture is cooled to 45-50 ℃ and discharged, and the silicon core layer mixture is obtained for standby;
s2: mixing modified high-density polyethylene and functional filler according to the proportion, adding color master batch, antioxidant, anti-aging agent and stabilizer, placing in a high-speed mixer, stirring and mixing at 120-130 ℃ for 40-50min, cooling to 45-50 ℃ and discharging to obtain an outer protective layer mixture for later use;
s3: and (3) respectively placing the silicon core layer mixture prepared in the steps S1 and S2 and the outer protective layer mixture into two single-screw extruders, and synchronously extruding by adopting a double-machine co-extruder head to obtain the silicon core pipe.
Further, the preparation method of the modified high-density polyethylene comprises the following steps: and dissolving dicumyl peroxide in acetone, adding diethyl allylmalonate, an antioxidant, zinc dimethyldithiocarbamate and high-density polyethylene, stirring and mixing uniformly, heating to 50-60 ℃, preserving heat until the acetone is completely volatilized, heating to 170-185 ℃, preserving heat, melting and processing for 15-20min, and obtaining the product, crushing and granulating to obtain the modified high-density polyethylene.
Further, the preparation method of the functional filler comprises the following steps: collecting polyethylene nanofibers to form bundles to obtain nanofiber bundles, winding the obtained nanofiber bundles on the surface of white carbon black to obtain composite particles, stirring and dispersing the composite particles in ethanol solution, adding a silane coupling agent, stirring and reacting for 20-24 hours, heating to 80 ℃, dropwise adding styrene under stirring, adding azodiisobutyronitrile as an initiator, carrying out heat preservation and reacting for 5-8 hours under nitrogen atmosphere, centrifuging after the reaction is completed, washing a filter cake with absolute ethanol for three times, and drying to obtain the functional filler.
The invention has the beneficial effects that:
according to the silicon core tube resistant to environmental stress cracking, disclosed by the invention, the high-density polyethylene is modified, and meanwhile, the functional filler is added for synergistic effect, so that the stress cracking resistance of the prepared silicon core tube can be improved, and the service life is longer.
Detailed Description
The present invention will be described in detail with reference to the following specific examples:
example 1
Preparation of functional fillers
Collecting polyethylene nanofibers to form bundles to obtain nanofiber bundles, winding the obtained nanofiber bundles on the surface of white carbon black to obtain composite particles, stirring and dispersing the composite particles in 95wt% ethanol solution according to a solid-to-liquid ratio of 15g/L, adding a silane coupling agent with the molar mass of 1/10 white carbon black, stirring and reacting for 24 hours, heating to 80 ℃, dropwise adding styrene with the mass of 4 times white carbon black under the stirring condition, adding azobisisobutyronitrile with the mass of 1/10 white carbon black as an initiator, carrying out heat preservation and reacting for 6 hours under nitrogen atmosphere, centrifuging after the reaction is completed, washing a filter cake with absolute ethanol for three times, and drying to obtain the functional filler.
Preparation of modified high density polyethylene
Dissolving 0.1 part by weight of dicumyl peroxide in acetone with the mass of 10 times of that of the dicumyl peroxide, adding 0.5 part by weight of diethyl allylmalonate, 0.2 part by weight of antioxidant and 0.1 part by weight of zinc dimethyldithiocarbamate and 100 parts by weight of high-density polyethylene, uniformly stirring and mixing, heating to 60 ℃, preserving heat until the acetone is completely volatilized, heating to 185 ℃, preserving heat, melting and processing for 20 minutes, and obtaining the product, namely crushing and granulating to obtain the modified high-density polyethylene.
Preparation of silicon core tube
S1: according to the proportion, 30 parts by weight of carrier resin high-density polyethylene is taken in total, 15 parts by weight of carrier resin high-density polyethylene is firstly taken and placed in a high-speed stirrer, 50 parts by weight of silicone resin and 8 parts by weight of oleamide are added, after the temperature is raised to 100 ℃ and evenly stirred, the temperature is raised to 120 ℃, 3 parts by weight of compatilizer and 2 parts by weight of lubricant polyethylene wax are added, the mixture is stirred at a high speed for 20 minutes while keeping the temperature, 5 parts by weight of flame retardant FR-302C, 2 parts by weight of antioxidant 1010 and the rest of carrier resin are added, the mixture is stirred for 30 minutes continuously, heating is stopped, and the mixture is stirred continuously until the mixture is cooled to 50 ℃ and discharged, so that the silicon core layer mixture is obtained for standby;
a2: according to the proportion, 90 parts of high-density polyethylene and 15 parts of functional filler are taken, stirred and mixed uniformly, 5 parts of color master batch, 3 parts of antioxidant tri (2, 4-di-tert-butyl) phenyl phosphite, 3 parts of antioxidant 2, 4-trimethyl-1, 2-dihydroquinoline and 2 parts of stabilizer isooctyl dithioacetate di-n-octyl tin are added, and placed in a high-speed stirrer, stirred and mixed for 50 minutes at 130 ℃, cooled to 50 ℃ and discharged to obtain an outer protective layer mixture for standby;
s3: the silicon core layer mixture and the outer protective layer mixture prepared in the steps S1 and S2 are respectively placed in two single-screw extruders, a double-machine co-extruder head is adopted, and the technological parameters of the single-screw extruder for the silicon core layer are as follows: at the die temperature of 198 ℃, the screw rotating speed of 63r/min and the traction speed of 6m/min, the technological parameters of the single screw extruder with the outer protective layer are as follows: synchronously extruding to obtain the silicon core tube with the thickness of the silicon core layer of 0.2mm and the thickness of the outer protective layer of 2mm under the conditions that the die temperature is 198 ℃, the screw rotating speed is 76r/min and the traction speed is 6 m/min.
Example two
Preparation of functional fillers
Collecting polyethylene nanofibers to form bundles to obtain nanofiber bundles, winding the obtained nanofiber bundles on the surface of white carbon black to obtain composite particles, stirring and dispersing the composite particles in 95wt% ethanol solution according to the solid-to-liquid ratio of 12g/L, adding silane coupling agent with the molar mass of 1/10 white carbon black, stirring and reacting for 22 hours, heating to 80 ℃, dropwise adding styrene with the mass of 5 times white carbon black under the stirring condition, adding azodiisobutyronitrile with the mass of 1/10 white carbon black as an initiator, carrying out heat preservation and reacting for 8 hours under the nitrogen atmosphere, centrifuging after the reaction is completed, washing a filter cake with absolute ethanol for three times, and drying to obtain the functional filler.
Preparation of modified high density polyethylene
Dissolving 0.14 weight part of dicumyl peroxide in acetone with the mass of 10 times of dicumyl peroxide, adding 0.8 weight part of diethyl allylmalonate, 0.1 weight part of antioxidant and 0.1 weight part of zinc dimethyldithiocarbamate and 100 weight parts of high-density polyethylene, uniformly stirring and mixing, heating to 55 ℃, preserving heat until the acetone is completely volatilized, heating to 175 ℃, preserving heat, melting and processing for 15min, and obtaining the product, namely crushing and granulating to obtain the modified high-density polyethylene.
Preparation of silicon core tube
S1: according to the proportion, taking 25 parts by weight of carrier resin high-density polyethylene in total, firstly taking 12 parts by weight of carrier resin high-density polyethylene, placing the carrier resin high-density polyethylene in a high-speed stirrer, adding 55 parts by weight of silicone resin and 10 parts by weight of oleamide, heating to 95 ℃, stirring uniformly, heating to 115 ℃, adding 2 parts by weight of compatilizer and 2 parts by weight of lubricant polyethylene wax, carrying out high-speed stirring at a constant temperature for 15min, adding 2 parts by weight of flame retardant FR-302C, 3 parts by weight of antioxidant 1010 and the rest carrier resin, continuously stirring for 25min, stopping heating, continuously stirring until the mixture is cooled to 50 ℃, and discharging to obtain a silicon core layer mixture for standby;
a2: according to the proportion, 80 parts of high-density polyethylene and 12 parts of functional filler are taken, stirred and mixed uniformly, 2 parts of color master batch, 2 parts of antioxidant tri (2, 4-di-tert-butyl) phenyl phosphite, 2 parts of antioxidant 2, 4-trimethyl-1, 2-dihydroquinoline and 1 part of stabilizer isooctyl dithioglycolate di-n-octyl tin are added, and placed in a high-speed stirrer, stirred and mixed for 40min at 125 ℃, cooled to 45 ℃ and discharged to obtain an outer protective layer mixture for standby;
s3: the silicon core layer mixture and the outer protective layer mixture prepared in the steps S1 and S2 are respectively placed in two single-screw extruders, a double-machine co-extruder head is adopted, and the technological parameters of the single-screw extruder for the silicon core layer are as follows: the die temperature is 195 ℃, the screw rotating speed is 60r/min, the traction speed is 5m/min, and the technological parameters of the single screw extruder with the outer protective layer are as follows: synchronously extruding to obtain the silicon core tube with the thickness of the silicon core layer of 0.3mm and the thickness of the outer protective layer of 3mm under the conditions that the temperature of the die is 195 ℃, the rotating speed of the screw is 75r/min and the traction speed is 5 m/min.
Example III
Preparation of functional fillers
Collecting polyethylene nanofibers to form bundles to obtain nanofiber bundles, winding the obtained nanofiber bundles on the surface of white carbon black to obtain composite particles, stirring and dispersing the composite particles in 95wt% ethanol solution according to a solid-to-liquid ratio of 10g/L, adding a silane coupling agent with the molar mass of 1/10 white carbon black, stirring and reacting for 20 hours, heating to 80 ℃, dropwise adding styrene with the mass of 4 times white carbon black under the stirring condition, adding azobisisobutyronitrile with the mass of 1/10 white carbon black as an initiator, carrying out heat preservation and reacting for 5 hours under nitrogen atmosphere, centrifuging after the reaction is completed, washing a filter cake with absolute ethanol for three times, and drying to obtain the functional filler.
Preparation of modified high density polyethylene
Dissolving 0.12 weight part of dicumyl peroxide in acetone with the mass of 10 times of dicumyl peroxide, adding 0.6 weight part of diethyl allylmalonate, 0.1 weight part of antioxidant and 0.1 weight part of zinc dimethyldithiocarbamate and 100 weight parts of high-density polyethylene, uniformly stirring and mixing, heating to 60 ℃, preserving heat until the acetone is completely volatilized, heating to 170 ℃, preserving heat, melting and processing for 20 minutes, and obtaining the product, namely crushing and granulating to obtain the modified high-density polyethylene.
Preparation of silicon core tube
S1: according to the proportion, 20 parts by weight of carrier resin high-density polyethylene is taken in total, 10 parts by weight of carrier resin high-density polyethylene is firstly placed in a high-speed stirrer, 45 parts by weight of silicone resin and 5 parts by weight of oleamide are added, the temperature is raised to 90 ℃ and uniformly stirred, the temperature is raised to 115 ℃, 1 part by weight of compatilizer and 1 part by weight of lubricant polyethylene wax are added, the mixture is stirred at a high speed for 10 minutes while keeping the temperature, 3 parts by weight of flame retardant FR-302C, 1 part by weight of antioxidant 1010 and the rest carrier resin are added, stirring is continued for 20 minutes, heating is stopped, stirring is continued until the mixture is cooled to 45 ℃ and discharged, and the silicon core layer mixture is obtained for standby;
a2: according to the proportion, 75 parts of high-density polyethylene and 10 parts of functional filler are taken, stirred and mixed uniformly, 3 parts of color master batch, 1 part of antioxidant tri (2, 4-di-tert-butyl) phenyl phosphite, 1 part of antioxidant 2, 4-trimethyl-1, 2-dihydroquinoline and 1 part of stabilizer isooctyl dithioglycolate di-n-octyl tin are added, and placed in a high-speed stirrer, stirred and mixed for 45min at 120 ℃, cooled to 50 ℃ and discharged to obtain an outer protective layer mixture for standby;
s3: the silicon core layer mixture and the outer protective layer mixture prepared in the steps S1 and S2 are respectively placed in two single-screw extruders, a double-machine co-extruder head is adopted, and the technological parameters of the single-screw extruder for the silicon core layer are as follows: the die temperature is 200 ℃, the screw rotating speed is 65r/min, the traction speed is 7m/min, and the technological parameters of the single screw extruder with the outer protective layer are as follows: synchronously extruding to obtain the silicon core tube with the thickness of the silicon core layer of 0.2mm and the thickness of the outer protective layer of 3mm under the conditions that the die temperature is 200 ℃, the screw rotating speed is 80r/min and the traction speed is 7 m/min.
Comparative example one
This example differs from example one in that this comparative example uses a conventional high density polyethylene instead of a modified high density polyethylene.
Comparative example two
This example differs from example one in that white carbon black was directly added to replace the functional filler.
The silicon core tubes prepared in the first embodiment to the third embodiment, the first comparative embodiment and the second comparative embodiment are subjected to mechanical property test and environmental stress cracking resistance test, and the test results are shown in the following table:
| testing performance | Example 1 | Example two | Example III | Comparative example one | Comparative example two |
| Elongation at break/% | 398 | 394 | 395 | 374 | 382 |
| Tensile Strength/MPa | 28.36 | 29.11 | 27.98 | 22.34 | 23.18 |
| Flexural Strength/MPa | 20.15 | 21.87 | 20.54 | 16.21 | 17.18 |
| Notched impact strength (KJ.m2) | 65.42 | 66.39 | 64.17 | 54.29 | 57.58 |
| Environmental stress cracking resistance time/h | 321 | 296 | 317 | 87 | 95 |
As can be seen from the table, the modified high-density polyethylene and the functional filler added into the silicon core tube outer protective layer can effectively improve the mechanical property and the environmental stress cracking resistance of the silicon core tube, and have the best effect when the silicon core tube outer protective layer and the silicon core tube outer protective layer are used together.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention. The technology, shape, and construction parts of the present invention, which are not described in detail, are known in the art.
Claims (8)
1. The silicon core pipe resistant to environmental stress cracking is characterized by comprising a synchronously extruded composite silicon core layer and an outer protective layer, wherein the outer protective layer comprises the following raw materials in parts by weight: 75-90 parts of modified high-density polyethylene, 2-5 parts of color master batch, 10-15 parts of functional filler, 1-3 parts of antioxidant, 1-3 parts of anti-aging agent and 1-2 parts of stabilizer, wherein the modified high-density polyethylene is allyl diethyl malonate melt grafting modified high-density polyethylene;
the functional filler takes white carbon black as a core, a styrene outer layer is wrapped outside the core, a fiber layer is arranged between the polystyrene outer layer and the core, the fiber layer is formed by wrapping polyethylene nano fibers, and the thickness is 0.1-0.12mm;
the preparation method of the functional filler comprises the following steps: collecting polyethylene nanofibers to form bundles to obtain nanofiber bundles, winding the obtained nanofiber bundles on the surface of white carbon black to obtain composite particles, stirring and dispersing the composite particles in ethanol solution, adding a silane coupling agent, stirring and reacting for 20-24 hours, heating to 80 ℃, dropwise adding styrene under stirring, adding azodiisobutyronitrile as an initiator, carrying out heat preservation and reacting for 5-8 hours under nitrogen atmosphere, centrifuging after the reaction is completed, washing a filter cake with absolute ethanol for three times, and drying to obtain the functional filler.
2. The silicon core tube resistant to environmental stress cracking as set forth in claim 1, wherein the outer protective layer comprises the following raw materials in parts by weight: 80 parts of modified high-density polyethylene, 2 parts of color master batch, 12 parts of functional filler, 2 parts of antioxidant, 2 parts of anti-aging agent and 1 part of stabilizer.
3. The silicon core tube resistant to environmental stress cracking as set forth in claim 1, wherein the silicon core layer comprises the following raw materials in parts by weight: 20-30 parts of carrier resin, 45-55 parts of silicone resin, 5-10 parts of oleamide, 1-2 parts of lubricant, 2-5 parts of flame retardant FR-302C, 1-3 parts of compatilizer and 10101-3 parts of antioxidant.
4. A silicon core tube resistant to environmental stress cracking according to claim 3, wherein said silicon core layer comprises the following raw materials in parts by weight: 30 parts of carrier resin, 50 parts of silicone resin, 8 parts of oleamide, 2 parts of lubricant, 5 parts of flame retardant FR-302C, 3 parts of compatilizer and 10102 parts of antioxidant.
5. The silicon core tube resistant to environmental stress cracking according to claim 4, wherein said stabilizer is isooctyl dimercaptoacetate di-n-octyl tin, said lubricant is polyethylene wax, said antioxidant is phenyl tris (2, 4-di-t-butyl) phosphite, and said anti-aging agent is 2, 4-trimethyl-1, 2-dihydroquinoline.
6. The silicon core tube of claim 5, wherein the thickness of the silicon core layer is 0.2-0.3mm and the thickness of the outer protective layer is 2-3mm.
7. The method for preparing an environmental stress crack resistant silicon core tube as defined in any one of claims 1 to 6, wherein the method for preparing the silicon core tube comprises the steps of:
s1: according to the proportion, 1/2 mass of carrier resin is put into a high-speed stirrer, silicone resin and oleamide are added, the temperature is raised to 90-100 ℃ and stirred uniformly, then the temperature is raised to 115-120 ℃, compatilizer and lubricant are added, the high-speed stirring is carried out for 10-20min at a high temperature, flame retardant, antioxidant 1010 and the rest carrier resin are added, the stirring is continued for 20-30min, the heating is stopped, the stirring is continued until the mixture is cooled to 45-50 ℃ and discharged, and the silicon core layer mixture is obtained for standby;
s2: mixing modified high-density polyethylene and functional filler according to the proportion, adding color master batch, antioxidant, anti-aging agent and stabilizer, placing in a high-speed mixer, stirring and mixing at 120-130 ℃ for 40-50min, cooling to 45-50 ℃ and discharging to obtain an outer protective layer mixture for later use;
s3: and (3) respectively placing the silicon core layer mixture prepared in the steps S1 and S2 and the outer protective layer mixture into two single-screw extruders, and synchronously extruding by adopting a double-machine co-extruder head to obtain the silicon core pipe.
8. The method for preparing the silicon core tube resistant to environmental stress cracking according to claim 7, wherein the preparation method of the modified high-density polyethylene is as follows: and dissolving dicumyl peroxide in acetone, adding diethyl allylmalonate, an antioxidant, zinc dimethyldithiocarbamate and high-density polyethylene, stirring and mixing uniformly, heating to 50-60 ℃, preserving heat until the acetone is completely volatilized, heating to 170-185 ℃, preserving heat, melting and processing for 15-20min, and obtaining the product, crushing and granulating to obtain the modified high-density polyethylene.
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